CN102899679B - Utilize gypsum mineralising CO 2the method of co-producing sulfuric acid - Google Patents
Utilize gypsum mineralising CO 2the method of co-producing sulfuric acid Download PDFInfo
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- CN102899679B CN102899679B CN201210410498.XA CN201210410498A CN102899679B CN 102899679 B CN102899679 B CN 102899679B CN 201210410498 A CN201210410498 A CN 201210410498A CN 102899679 B CN102899679 B CN 102899679B
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- gypsum
- sulfuric acid
- mineralising
- electrolyte
- producing sulfuric
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Abstract
The invention discloses one and utilize gypsum mineralising CO
2the method of co-producing sulfuric acid: anion-exchange membrane is placed in electrolyzer, electrolyzer is made to be divided into positive polar region and negative pole district, the metabisulfite solution as electrolyte liquid is added in negative pole district, positive pole adds the sulphuric acid soln as anode electrolyte, the gypsum of pulverizing is joined in the electrolyte liquid of electrolyzer, be filled with carbon dioxide simultaneously, direct supply is applied between anode electrode and negative electrode, reducing hydrogen ions in electrolyte liquid is hydrogen by negative electrode, the carbon dioxide conversion in solution is made to be carbonate, carbonate and gypsum generation replacement(metathesis)reaction, gypsum is converted into calcium carbonate, displace free-pouring sulfate radical simultaneously, sulfate radical under galvanic action through anion-exchange membrane, be combined with the hydrogen ion that anode electrode produces and generate sulfuric acid.The advantages such as it is high that the present invention has product added value, and technical process is simple, and reaction conditions is gentle.
Description
Technical field
The present invention relates to a kind of CO
2mineralising discharge-reducing method, particularly one utilizes gypsum mineralising CO
2generate the CO of sulfuric acid
2discharge-reducing method.
Background technology
Climate warming has been the mathematical fact, and the possibility of more than 90% is that mankind's activity causes.CO in global atmosphere
2mass concentration is by 280 × 10 before industrial age
-6increase to 379 × 10 in 2005
-6.The greenhouse gas emission produced due to mankind's activity increases gradually, expects 2100, the CO in air
2mass concentration will reach 570 × 10
-6, cause Global Temperature to raise 1.9 DEG C, sea-level rise 38 cm.Must reduce by 6,000,000,000 tons of CO every year in global range
2discharge really could prevent global warming.The maximum living environment problem that air " Greenhouse effect " and global warming will be 21 century facing mankind.The mankind produce and the CO that directly discharge is a large amount of in energy resource system
2it is the major cause causing this phenomenon to produce.No matter consider from environment protection or from the angle of resource recycling, to the CO of discharge in worldwide
2carry out catching the very urgent task that utilization (CCU) is facing mankind.
At present, traditional CO
2application way is by CO
2be converted into the Chemicals such as urea and methyl alcohol, but by CO
2be converted into the CO of Chemicals
2consumption is very limited, and a large amount of carbonic acid gas still directly discharges air, in order to reduce CO
2be discharged into the amount of air, in recent years, have developed CO
2be converted into the novel method of organism or polymkeric substance.But these methods are owing to reducing discharging CO
2amount less, thus energy consumption height is not extensively promoted.Therefore, people need to develop new reduction of discharging CO
2method.
Utilize mineral mineralising CO
2, the Chemicals simultaneously obtaining high added value are a kind of CO
2utilize novel method (CMU).Contriver is at CO
2mineralising field has compared deep research, successively develops and completes " the CO of the rich potassium solution of coproduction
2mineralization methods ", " CO of the rich potassium solution of pyroprocess coproduction
2mineralization methods " and " CO of the rich potassium solution of catalysis method coproduction
2mineralization methods ", at CO
2in mineralisation process, the rich potassium solution of coproduction, is CO
2contribution has been made in the production that mineralising has reduced discharging potash fertilizer.These methods have applied for Chinese invention patent.But these completed CO
2mineralization methods is not enough, and place is that technical process is longer, and energy consumption is higher.
Gypsum (CaSO
42H
2o) be topmost vitriol on the earth, the plaster of paris is extensively present in sedimentogeneous rock, rich reserves.In addition, waste gypsum main component is calcium sulfate, in the production process of the industries such as phosphoric acid, has a large amount of gypsum as industrial waste to produce every year, and only China just has approximately just has 5,000 ten thousand tons of discharges every year, and the phosphogypsum total amount of piling up at present is more than 500,000,000 tons.The accumulation of a large amount of waste gypsum not only occupies tract, and can polluted-water and soil.Owing to effectively not utilizing the method for calcium sulfate in waste gypsum at present, the waste gypsum of bulk deposition has compromised agriculture production, livestock growth and breeding and HUMAN HEALTH, becomes environmental problem urgently to be resolved hurrily.But contain 18.6% element sulphur in gypsum, and China's Sulphur ressource is very deficient.Gypsum is discharged as solid waste, not only causes environmental pollution, and waste valuable Sulphur ressource.Therefore, more efficientlyly both CO can be eliminated in the urgent need to developing
2and waste gypsum, again can the novel method of valuable Sulphur ressource in efficient recovery waste gypsum.
Summary of the invention:
For the deficiency that prior art exists, object of the present invention aims to provide a kind of new CO
2application way---utilize gypsum mineralising CO
2co-producing sulfuric acid, to solve prior art CO
2the technical process that mineralization methods exists is long, the problems such as energy consumption is higher, thus realizes the pollution eliminating CO2 and waste gypsum, reclaims valuable Sulphur ressource.
Basic ideas of the present invention are by by CO
2the methods combining of mineralising and film electrolysis, realizes CO
2with the mineralising of gypsum, produce and be separated sulfuric acid, thus breaking thermodynamic(al)equilibrium, in low voltage, realizing under normal temperature and pressure utilizing weakly acidic CO
2produce the chemical process of highly acid sulfuric acid.
What the present invention proposed utilizes gypsum mineralising CO
2the method of co-producing sulfuric acid, its main contents are: anion-exchange membrane is placed in electrolyzer, electrolyzer is made to be divided into positive polar region and two, negative pole district part, the metabisulfite solution as electrolyte liquid is added in negative pole district, positive pole adds the sulphuric acid soln as anode electrolyte, powder gypsum is joined in the electrolyte liquid of electrolyzer, be filled with carbon dioxide simultaneously, direct supply is applied between anode electrode and negative electrode, reducing hydrogen ions in negative electrode liquid is hydrogen by negative electrode, the carbon dioxide conversion in solution is made to be carbonate, carbonate and gypsum generation replacement(metathesis)reaction, gypsum is converted into calcium carbonate, displace free-pouring sulfate radical simultaneously, sulfate radical under galvanic action through anion-exchange membrane, be combined with the hydrogen ion that anode electrode produces and generate sulfuric acid.
In technique scheme, the hydrogen ion that described anode electrode produces can be produced by gas diffusion electrode oxidizes hydrogen gas, and the hydroxide radical that also can be oxidized in anode electrode liquid by metal foil electrodes produced.The hydrogen that gas diffusion electrode is oxidized preferably comes from the hydrogen that negative electrode produces, and certainly, also can come from other place.
In technique scheme, described gypsum can be the plaster of paris ore of occurring in nature, and the main component that also can be Industrial processes generation is the industrial product of gypsum, as the waste gypsum produced in production process of phosphoric acid.
In technique scheme, the gypsum added in electrolyte liquid is generally powder gypsum, and its particle size is at least less than 10 object gypsum powders.
In technique scheme, the concentration of anode electrolyte sulfuric acid controls to be 0.01 mol/L to 5 mol/L usually, and the concentration of electrolyte molten sulfur acid sodium solution is 0.1 mol/L to 5 mol/L.
In technique scheme, negative electrode material can be metal platinum, palladium metal or metallic nickel.
In technique scheme, during the hydrogen source of the hydrogen utilizing negative pole to produce as positive gas diffusion electrode, gypsum and CO
2there is mineralising reaction as follows:
CaSO
42H
2O + CO
2→ CaCO
3+ H
2SO
4+ H
2O (1)
In essence, this is the replacement(metathesis)reaction that " weak acid carbonic acid " produces " strong acid sulfuric acid ", and the chemical reaction rule of " strong acid weak acid " that this and people know is contrary.Calculation of thermodynamics also shows, the Gibbs free energy () of this reaction under standard state (25 DEG C, 1atm) is 85.12 kJ/mol(> 50 kJ/mol).This means, the chemical process of this " weak acid strong acid " can not spontaneously be carried out.
The gypsum mineralising CO that the present invention proposes
2the novel method of co-producing sulfuric acid, solves gypsum mineralising CO
2in process, " weak acid strong acid " can not the spontaneous sciences problems carried out, and achieves and utilizes weakly acidic CO
2produce highly acid sulfuric acid, break the conventional thought of " strong acid weak acid ".Under certain conditions, this process only needs the voltage of 0.8V just can carry out, and the realization of this process, makes less energy-consumption, low cost, efficiency utilization CO
2become possibility, for solving global CO
2reduction of discharging problem provides a kind of important method.
The gypsum mineralising CO that the present invention proposes
2the novel method of co-producing sulfuric acid, abundant raw material source, added value of product is high.The waste gypsum of plaster of paris ore or industrial output, all can adopt the method mineralising CO that the present invention proposes
2.Product sulfuric acid is not only the raw material of numerous Chemicals, but also is widely used in other sector of the national economy, and calcium carbonate is widely used in coating, cement and foodstuff additive; And the process problem of the waste gypsum of people is perplexed in breakthrough process for a long time, solves an environmental pollution difficult problem while effectively utilizing waste resource, the road numerous industries of generation waste gypsum being moved towards develop in a healthy way.
Accompanying drawing explanation
When Fig. 1 is anode electrode employing gas diffusion electrode, gypsum mineralising CO
2co-producing sulfuric acid schematic diagram
When Fig. 2 is anode electrode employing metal electrode, gypsum mineralising CO
2co-producing sulfuric acid schematic diagram
1---gas diffusion electrode (positive pole), 2---anion-exchange membrane, 3---negative metal electrode, 4---hydrogen gas buffer, 5---metal foil electrodes (positive pole)
Embodiment
Below in conjunction with accompanying drawing, by embodiment, the present invention is described in further detail.It is important to point out; following examples are only for the present invention is described further; limiting the scope of the invention can not be interpreted as; affiliated art skilled staff is according to foregoing invention content; some nonessential improvement are made to the present invention and adjustment is specifically implemented; be very easy to accomplish, therefore, such improvement still should belong to protection scope of the present invention with adjustment.
Embodiment 1
The mineralisation process of the present embodiment as shown in Figure 1.Electrolyzer by only allowing anion-permeable, and can stop the anion-exchange membrane 2 of cation permeable to be divided into positive and negative two regions.Add the H of 0.2mol/L
2sO
4as anode electrolyte in solution to anolyte groove, add the Na of 1.2mol/L
2sO
4as electrolyte liquid in solution to electrolyte groove.Anode electrode adopts gas diffusion electrode 1, and negative electrode adopts platinum electrode 3.Weighing 3g dried gypsum adds in electrolyte liquid, at the CO that electrolyte trench bottom bubbling passes into
2flow is 20 ml/min, and the Hydrogen collection that negative electrode is produced also is entered surge tank 4, passes into gas diffusion electrode, under the voltage of 1.5V, carry out electrolytic reaction 1 h from the hydrogen in surge tank.Electrolyte groove solid electrolytic product is dried, obtains containing CO
2the solid of mineralization product calcium carbonate.Sulfuric acid concentration in anode electrode liquid is increased to 0.7 mol/L.The current efficiency of producing calcium carbonate is 94.1%, and the current efficiency of producing sulfuric acid is 95.1%.
Embodiment 2
The mineralisation process of the present embodiment as shown in Figure 1.Electrolyzer by only allowing anion-permeable, and can stop the anion-exchange membrane 2 of cation permeable to be divided into positive and negative two regions.Add the H of 0.1mol/L
2sO
4as anode electrolyte in solution to anolyte groove, add the Na of 1.5mol/L
2sO
4as electrolyte liquid in solution to electrolyte groove.Anode electrode adopts gas diffusion electrode 1, and negative electrode adopts platinum electrode 3.Weighing the dry phosphogypsum solid waste of 5g adds in electrolyte liquid, at the CO that electrolyte trench bottom bubbling passes into
2flow is 20 ml/min, and the Hydrogen collection that negative electrode is produced also is entered surge tank 4, passes into gas diffusion electrode from the hydrogen in surge tank, under the voltage of 2.6V, carries out electrolytic reaction 1 h. and is dried by electrolyte groove solid electrolytic product, obtain containing CO
2the solid of mineralization product calcium carbonate.Sulfuric acid concentration in anode electrode liquid is increased to 1.5 mol/L.The current efficiency of producing calcium carbonate is 94.5%, and the current efficiency of producing sulfuric acid is 94.7%
Embodiment 3
The mineralisation process of the present embodiment as shown in Figure 2.Electrolyzer by only allowing anion-permeable, and can stop the anion-exchange membrane 2 of cation permeable to be divided into positive and negative two regions.Add the H of 0.1 mol/L
2sO
4as anode electrolyte in solution to anolyte groove, add the Na of 1 mol/L
2sO
4as electrolyte liquid in solution to electrolyte groove.Anode electrode adopts metal foil electrodes 5, and negative electrode adopts metallic nickel electrode 3.Weighing 3g dried gypsum adds in electrolyte liquid, at the CO that electrolyte trench bottom bubbling passes into
2flow is 20 ml/min, under the voltage of 2.6 V, carries out electrolytic reaction 1 h.Electrolyte groove solid electrolytic product is dried, obtains containing CO
2the solid of mineralization product calcium carbonate, the sulfuric acid concentration in anode electrode liquid is increased to 0.85 mol/L.The current efficiency of producing calcium carbonate is 94.2%, and the reaction efficiency producing sulfuric acid is 94.5%.
Claims (10)
1. one kind utilizes gypsum mineralising CO
2the method of co-producing sulfuric acid, it is characterized in that: anion-exchange membrane is placed in electrolyzer, electrolyzer is made to be divided into positive polar region and negative pole district, the metabisulfite solution as electrolyte liquid is added in negative pole district, positive pole adds the sulphuric acid soln as anode electrolyte, the gypsum of pulverizing is joined in the electrolyte liquid of electrolyzer, be filled with carbon dioxide simultaneously, direct supply is applied between anode electrode and negative electrode, reducing hydrogen ions in electrolyte liquid is hydrogen by negative electrode, the carbon dioxide conversion in solution is made to be carbonate, carbonate and gypsum generation replacement(metathesis)reaction, gypsum is converted into calcium carbonate, displace free-pouring sulfate radical simultaneously, sulfate radical under galvanic action through anion-exchange membrane, be combined with the hydrogen ion that anode electrode produces and generate sulfuric acid, the hydrogen ion that described anode electrode produces produced by anode electrode oxidizes hydrogen gas, hydrogen comes from the hydrogen that negative electrode produces, described anode electrode is gas diffusion electrode.
2. according to claim 1ly utilize gypsum mineralising CO
2the method of co-producing sulfuric acid, is characterized in that: the described mode being filled with carbon dioxide is that bubbling is filled with.
3. according to claim 1 and 2ly utilize gypsum mineralising CO
2the method of co-producing sulfuric acid, is characterized in that: described gypsum is the plaster of paris ore of occurring in nature, or for Industrial processes produce main component be the industrial product of gypsum.
4. according to claim 1 and 2ly utilize gypsum mineralising CO
2the method of co-producing sulfuric acid, is characterized in that: described pulverizing gypsum is that particle size is at least less than 10 object gypsum powders.
5. according to claim 3ly utilize gypsum mineralising CO
2the method of co-producing sulfuric acid, is characterized in that: described pulverizing gypsum is that particle size is at least less than 10 object gypsum powders.
6. according to claim 1 and 2ly utilize gypsum mineralising CO
2the method of co-producing sulfuric acid, is characterized in that: the concentration of described anode electrolyte sulfuric acid is 0.01mol/L to 5mol/L, and the concentration of electrolyte molten sulfur acid sodium solution is 0.1mol/L to 5mol/L.
7. according to claim 5ly utilize gypsum mineralising CO
2the method of co-producing sulfuric acid, is characterized in that: the concentration of described anode electrolyte sulfuric acid is 0.01mol/L to 5mol/L, and the concentration of electrolyte molten sulfur acid sodium solution is 0.1mol/L to 5mol/L.
8. according to claim 1 and 2ly utilize gypsum mineralising CO
2the method of co-producing sulfuric acid, is characterized in that: described negative electrode material is metal platinum, palladium metal or metallic nickel.
9. according to claim 5ly utilize gypsum mineralising CO
2the method of co-producing sulfuric acid, is characterized in that: described negative electrode material is metal platinum, palladium metal or metallic nickel.
10. according to claim 7ly utilize gypsum mineralising CO
2the method of co-producing sulfuric acid, is characterized in that: described negative electrode material is metal platinum, palladium metal or metallic nickel.
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| CN102899679B true CN102899679B (en) | 2015-08-19 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978653A (en) * | 2012-11-30 | 2013-03-20 | 四川大学 | Method for membrane electrolysis of mineralized CO2 co-produced strong acid |
| CN103952747A (en) * | 2014-04-15 | 2014-07-30 | 株洲冶炼集团股份有限公司 | Electro-deposition device for composite lead-carbon material |
| CN103966622A (en) * | 2014-04-30 | 2014-08-06 | 四川大学 | Method for realizing separation of potassium-rich solution through hydrochloric acid coproduced by utilizing membrane electrolysis technology to mineralize CO2 |
| CN104591100A (en) * | 2015-01-15 | 2015-05-06 | 贵州大学 | Method for preparing sulphuric acid from ardealite by membrane separation method |
| CN106757119B (en) * | 2016-12-09 | 2019-02-26 | 大连理工大学 | One kind is for realizing CO2The electro-chemical systems that capture is sealed up for safekeeping with mineralising |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070958A (en) * | 1991-09-13 | 1993-04-14 | 帝国化学工业公司 | Electrochemical method |
| CN101481096A (en) * | 2009-02-19 | 2009-07-15 | 四川大学 | Technological process for producing sulphuric acid from waste gypsum and carbon dioxide and implementing membrane coupled reactor thereof |
| CN102530889A (en) * | 2012-02-23 | 2012-07-04 | 四川大学 | Method for preparing sulfuric acid by reducing and decomposing gypsum with pyrite |
| CN102701798A (en) * | 2012-06-08 | 2012-10-03 | 四川大学 | Method for mineralizing CO2 and co-producing potassium-rich solution by catalysis method |
| CN102701253A (en) * | 2012-06-08 | 2012-10-03 | 四川大学 | CO2 mineralization method capable of co-producing potassium-enriched solution by high temperature method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0107612A3 (en) * | 1982-09-02 | 1985-12-27 | Eltech Systems Limited | Method of conditioning a porous gas-diffusion electrode |
| JPH05302192A (en) * | 1992-04-27 | 1993-11-16 | Tanaka Kikinzoku Kogyo Kk | Method for electrolyzing organic salt |
| JP3196382B2 (en) * | 1992-12-16 | 2001-08-06 | 東ソー株式会社 | Method for electrolysis of sodium sulfate solution |
| JPH11229168A (en) * | 1998-02-17 | 1999-08-24 | Mitsubishi Heavy Ind Ltd | Hydrogen peroxide generating device |
| JP2003506120A (en) * | 1999-08-05 | 2003-02-18 | ステリス インコーポレイテッド | Synthesis of peracetic acid by electrolysis. |
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2012
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070958A (en) * | 1991-09-13 | 1993-04-14 | 帝国化学工业公司 | Electrochemical method |
| CN101481096A (en) * | 2009-02-19 | 2009-07-15 | 四川大学 | Technological process for producing sulphuric acid from waste gypsum and carbon dioxide and implementing membrane coupled reactor thereof |
| CN102530889A (en) * | 2012-02-23 | 2012-07-04 | 四川大学 | Method for preparing sulfuric acid by reducing and decomposing gypsum with pyrite |
| CN102701798A (en) * | 2012-06-08 | 2012-10-03 | 四川大学 | Method for mineralizing CO2 and co-producing potassium-rich solution by catalysis method |
| CN102701253A (en) * | 2012-06-08 | 2012-10-03 | 四川大学 | CO2 mineralization method capable of co-producing potassium-enriched solution by high temperature method |
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